Textile printing



. or thioindigoid class (or,

' pared with the latter.

[ Patented a... 1.1938

mrao STATES PATENT OFFICE rux'rmcrnmrmo Richard Frank McQueen,

Goldstein and Simon Thomson Blackl r, En

gland, and David Alexander Whyte Fail-weather, Grangemonth, Scotland, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application May '1 Claims.

particularly of the indigoid and thioindigoid class. .A further object is to provide new and improved compositions especially suitable for this;

purpose. Other objects will appear hereinafter.

According to the invention we add water-sol-' ubie salts of anthraquinone sulfuric esters and/or sulphamic acids to printlngmfl es containing vat dyestuffs, particularly those of the indigoid if preferred, to the dyestuffs themselves previous to incorporation into i a printing paste) which facilitate reduction of --the dyestufis and are particularly valuable in that there is secured by their addition a better utilization of dyestufi. Thus, from printing pastes, for instance, such as are described in the i examples, one of which contains and the other does not contain an assistant according to the invention, but which are otherwise similar, the former will produce a print of greater depth of color and frequently of improved shade as com- Furthermore, the addition of these agents enables less reducing agent to be employed than would otherwise be the case.

As examples of-the water-soluble assistants employed may be mentioned soluble salts of betahydroxyanthraquinone sulfuric esters and of I anthraquinone beta-sulphamic acids. They may be incorporated at any stage in the production of the printing paste or added to the commercial color paste or powderwith or without other auxiliary agents, ,e. g., glycerin or the sodium. salt of the condensation product of formaldehyde and a sulfonated naphthalene.

- The foregoing assistants may be obtained by treating the appropriate beta-hydroxyanthraquinone or aminoanthraquinone, for instance, 2- hydroxyanthraquinone. 2:6- or 2:7-dihydroxyanthraquinone, Z-aminoanthraquinche -or 226-, or 2:7-diaminoanthraquinone. with pyridine-sulfur trioxide or pyridine chloro'sulfonic acid.

In addition to the defined sulfuric esters and sulphamic acids, we can also use substitution products, e. g., their halogen (chloro, bromo, etc.) and alkyl (methyl, ethyl and higher homologues) derivatives and the reduction products thereof still containing oxygen in the ms- (mesa-i po- 4, 1936 Serial In Great Britain May 8, 1935 sition or a mixture of any of these. The free esters and acids may be used because they are capable of being'converted into soluble salts by other auxiliary agents (e. g., alkali metal carbonates).

'I'hefollowing examples, in which the quantitles are stated in parts by weight, illustrate but do not limit the invention.

Example I A printing paste is made up of I Parts 10% aqueous paste of 6:6'-diethoxy thio indigo 100 Water. 100 British gum thickening 570 Glycerim 50 Formosul (sodium formaldehyde sulfoxylate I 80 Potassium carbonate 100 and to this paste are added 0.6 part of the sodium salt of the sulfuric ester of 2-hydroxyanthraqui none as a concentrated aqueous paste. After printing and drying. the goods are steamed for three to five minutes in the Mather-Flatt apparatus; rinsed. oxidized, rinsed and soaped. The printing paste fixes better and ,the print is of greater color strength than-is the case with a print produced in like manner but without the assistance of the sulfuric ester of 2-hydroxyanthraquinone. Similar results are obtained using the sodium salt of anthraquinone-2-sulphamic acid orof anthraquinone-zzii disulphamic acid. The sulfuric ester or sulphamic acid can be incorporated at any stage in the production of the printing paste.

Example I] A printing paste is made up of 36% aqueous paste of 5z7z5'z7f-tetrabromindigo prepared by ball milling the dyestuff with, water and 3% of a 10% paste Parts of sodium cellulose glycolate .,,.a 40 Water 7 w 160 British gum thickening 570 Glycerin 50 Sodium formaldehyde suifoxylate Potassium carbonate--.

- sulfuric ester of 2-hydroxyanthraquinone are added as a concentrated paste. Application and subsequent procedure are as in Example 1.

Example III A printing paste is made up of Parts 13% aqueous paste of 6:6-'-dichloro-4:4'-

dimethyl thioindigo 100 Water 100 British gum thickening 570 Glycerin-.. 50 Sodium formaldehyde slilfoxylateu Potassium carbonate and to 1000 parts of this paste are added 0.6 part of the sodium salt of the sulfuric ester of 2-hydroxyanthraquinone as a concentrated aqueous paste. Application and subsequent procedure are as in Example 1. Similar results are obtained using the sodium salt of. anthraquinone-2-sulphamic acid or of 2:6-disulphamic acid.

Other vat dyestufis may be used instead of those given inthe examples. As further exe. g., 4:4-dichloro-5:5'-dibromo indigo, 5;5'- dichloro-7:'l-dibromo indigo, bromo-Z-beta-naphthindol-Z-indolindigo, bis-alpha-naphthindolindigo, bis-beta-naphthindol indigo; thioindigos, e. g., 6:6'-dichloro-thioindigo, 6:6'-dimethoxy thioindigo, 6:6 -difluoro-thioindigo, 5:5 -dichloro-l :7 -dimethyl thioindigo, 5 z 5' -.dibromo- 7:7'-dimethyl thioindigo, 4:4'-dimethyl thioindigo, bis-beta-naphthionaphthene indigo, 5:5- dichloro-6 6' -dimethyl thioindigo, tetramethyl-S 5' -dichloro-thioindigo; thionaphthene indolindigos, e. g., 2-(5:7-dibromindol)- 2'-4:'l-dimethy1 thionaphthene indigo, 2-(5z7- dibromindol) -2'-6-chlor 7 methyl thionaphthene indigo, 2-(527-dibromindol) -2'-4:5:6:'ltetramethyl thionaphthene indigo; 2-(5z'l-dibromindol) -2' -4 "l-dimethyl-5-chloro thionaphthene indigo; aoenaphthene thionaphthene indigos, e. g., acenaphthene-4-ch1or-7-methyl thionaphthene indigo, thionaphthene acenaphthene indigo; 2Z3:2':3'-dianthraquinone indigo, dimethyl indirubin, dibromindirubin, water-insoluble reduction products of any of the aforesaid dyes, or related dyes. The invention. is also applicable to sulfur dyes.

The term "vat dyestuiP'is used to define dyes which are insoluble in water but which can be converted by heating with reducing agents and alkalis into soluble leuco compounds. The term indigoid is used generically as employed by Truttwin (1920).

amples may be mentioned indole in dolindigos,

Enzyklopadie der Kiipenfarbstofie In place of a part or all of the glycerin, another polyhydric alcohol may be used, c. g., di-

ethylene glycol. Likewise, the reducing agents, I

alkalis, and other auxiliary agents may be varied, e. g., by utilizing glucose, preservers syrup in place of sodium formaldehyde sulfoxylate, and other alkali metal carbonates in place of potassium carbonate. 'Othersoluble salts of the anthraquinone sulfuric esters or sulphamic acids, e'. g., the potassium salt, or ammonium salt may be used.

As many apparently widely difierent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. A vat dyestufi preparation suitable for use in printing textile fibers comprising a vat dyestuff, a compound selected-from the class consisting of anthraquinone sulphamic acids, watersolublesalts thereof, and such reduction products as contain oxygen in the meso-position.

2. A vat dye preparation comprising an indigoid dyestuff and a compound selected from the class consisting of anthraquinone sulphamic acids, water-soluble salts therebf, and such reduction products as contain oxygen in the mesoposition.

3. A vat dye preparation comprising an indigoid dyestufi and a soluble salt of an anthraquinone-beta-sulphamic acid.

4. The process which comprises printing textile materials with an indigoid vat dyestufi printing paste containing a vat dyestuff and a. soluble salt of a compound from the class consisting of anthraquinone sulphamic acids and such reduction products thereof as contain oxygen in the mesoposition.

5. The process which comprises printing textile materials with a. vat dyestuff printing paste comprising a vat dyestuff and an alkali metal salt of an, anthraquinone-beta-sulphamic acid.

6. The process which comprises printing on textile materials with a vat dyestufi printing paste comprising 6:6'-diethoxy thioindigo and an alkali metal salt of an anthraquinone-betasulphamic acid.

'7. A process which comprises printing textile materials with a. printing paste containing a vat dyestuii, a compound selected from the class consisting of anthraquinone sulphamic acids, water soluble salts thereof, and such reduction products as contain oxygen in the meso-position.

RICHARD FRANK GOLDSTEIN. SIMON THOMSON MCQUEEN. 

